Synthesis of hetero binuclear macrocyclic CoV complex bonded to chemically modified alumina support for oxidation of cyclohexane using oxygen

A binuclear complex M_A^IIM_B^IVL²⁺ [with M_A^II = Co^II and M_B^IV = V^IV] has been synthesized with a macrocyclic ligand prepared by condensing 2 equiv. of 2,6-diformyl-4-methylphenol with 2 equiv. of 1,2-phenylenediamine. This has been immobilized on a carbamate-modified alumina support by covalently binding it to the surface. The TGA analysis of the final catalyst showed that it is thermally stable up to 251 °C and it has been shown that it serves as a catalyst for oxidation of cyclohexane forming cyclohexanone and cyclohexanol in the ratio of 14:1 as identified by the GC/MS analysis.     

Manganeseporphyrins immobilized on silica microspheres as biomimetic catalysts hydroxylating cyclohexane with molecular oxygen

Three types of silica microspheres immobilizing Mn(III) porphyrins appending p-CH₃, p-H and p-Cl phenyl substituents (designated as MnMP-S-SiO₂, MnPP-S-SiO₂ and MnCP-S-SiO₂, respectively) have been synthesized and characterized using SEM, IR, UV-vis and TG. The SEM images show that the morphology of the silica microspheres is spheriform with ca. 2–4 μm diameter. The catalytic performances of various supported biomimetic catalysts for the hydroxylation of cyclohexane in the presence of molecular oxygen under mild conditions have been investigated and compared detailedly. The experimental results confirmed that the catalytic efficiencies of these silica microspheres are much higher than those of the free Mn(III) porphyrin analogues and follow the order of MnMP-S-SiO₂ > MnPP-S-SiO₂ > MnCP-S-SiO₂. All these results indicate that the grafting particles can not only protect metalloporphyrin from oxidation, but also promote it to activate O₂. They are mild, reusable and highly efficient heterogeneous catalyst for the epoxidation of cyclohexene. The effect of substituent groups was also discussed.     

Schiff base complex sol–gel method for LaCoO3 perovskite preparation with high-adsorbed oxygen

A novel Schiff base complex sol–gel method has been used to prepare LaCoO₃ producing high ratios of adsorbed (or surface) oxygen (α) to lattice oxygen (β). The as-prepared gels, characterized by Fourier transform infrared spectroscopy (FTIR), showed that both lanthanum and cobalt ions were complexed before calcinations. IR spectra revealed that CO₃²⁻ and NO₃⁻ presented on the sample surfaces during heat treatment. High-resolution transmission electron microscopic (HRTEM) images of all samples showed resolved lattice fringes with the inter-planar spacing 0.37–0.39 nm of the (0 1 2) plane in hexagonal perovskite. BET surface areas of LaCoO₃ nano-crystals were 11.7–18.6 m²/g. Ratios of adsorbed (or surface) oxygen (α) to lattice oxygen (β) quantified by X-ray photoemission spectroscopy showed that LaCoO₃ prepared by the Schiff base complex method produced higher ratios when bases had higher nitrogen content in molecules. Carbonate and nitrate which were resulting from the oxidation of functional groups in the Schiff base complex, can produce gaseous compounds and leave vacant sites for oxygen in the gas phase to adsorb.     

Alkaline earth cation-complexing chromatography with a neutral ligand chemically bonded to silica gel

Summary A sorbent based on a 3,6-dioxaoctanedioic acid diamide chemically bonded to silica gel has been prepared. Alkaline earth cation selectivity was observed and used to separate such ions.     

Redox characteristics of Schiff base manganese and cobalt complexes related to water-oxidizing complex of photosynthesis

In an effort to obtain synthetic analogues of water-oxidizing complex (WOC) of photosystem II (PS II) of plant photosynthesis, a Schiff base manganese and a cobalt complex, employing Niten, a SALEN type ligand, have been prepared. Cyclic and square wave voltammetric measurements have been performed to assess their redox characteristics. Both complexes undergo several reduction processes in cathodic negative potential region at more or less similar potentials. In view of these reductions being independent of the nature of the metal, they are thought to be ligand-localized. Although similar in negative region, a marked difference in the behavior of the complexes is observed in anodic region. While the cobalt complex is electrochemically inactive in the positive potentials up to +1.0 V vs. Ag/AgCl, the manganese complex displays two oxidation waves at +0.25 and +0.5 V vs. Ag/AgCl. The presence of oxidation wave in manganese complex at +0.5 V vs. Ag/AgCl or +0.7 V vs. NHE suggests that this complex can catalyze the oxidation of water and can, thus, simulate the WOC of PS II.     

Spectrophotometric studies of molecular complex formation between water-soluble cobalt(II) Schiff base complex and nucleotides in mixed solvent systems

The formation constants for 1:1 molecular complex formation between water-soluble cobalt(II) tetradentate Schiff base complex, disodium[{bis(4-methoxy-5-sulfo-salicylaldehyde)-4,5-dimethyl-o-phenylenediiminato}cobalt(II)], Na2[Co(SO3-4-meosal-4,5-dmophen)], and nucleotides, adenosine-5'-triphosphate (ATP) and cytidine-5'-triphosphate (CTP), in mixed solvent systems of ethanol and water with different volume fractions of ethanol and water have been determined spectrophotometrically at constant ionic strength (I = 0.2 mol dm(-3) NaClO4) and temperature 278 K. Trends in the values of formation constants according to the volume fractions of ethanol and water in ethanol and water mixed solvent systems, suggest that the trend of molecular complex formation increases with increasing the volume fraction of ethanol in mixed solvent systems.     

Ion-exchange properties of silica gel with covalently bonded histidine

The ion-exchange and acid-base properties of Silasorb 600 (10 μm) with immobilized histidine (His-SiO₂) were investigated. The acid-base properties of the sorbent were estimated from the dependence sof the retention of organic acids and bases on the eluent pH. The effect of various organic modifiers (benzoic, citric, oxalic, and sulfuric acids) and the eluent pH on the retention of inorganic ions was studied. It was shown that His-SiO₂ exhibits anion-exchange properties in acidic and weakly acidic media at pH < 5.7. Eight anions were separated under optimal conditions on a 150 × 4.6-mm column in 21 min using a 5 mM oxialic acid solution as an eluent.     

Solid phase extraction and preconcentration of some metal ions using Schiff base immobilised silica gel followed by ICP-OES

ABSTRACT

In this study, a simple and efficient solid phase extraction procedure was developed for simultaneous separation and preconcentration of Ba, Cd, Co, Cu, Mn and Ni. The methodology was based on preconcentration of the target analytes on N,N’-bis(4-methoxysalicylidene)-1,3-propanediamine modified silica gel prior to inductively coupled plasma optic emission spectrometry detection. The experimental conditions were as follows: pH of sample 5.00; sample and eluent flow rates 3 mL min^?1; sample volume 25 mL; eluent 0.5 mol L^?1 HNO₃; eluent volume 3.0 mL. Preconcentration factor was achieved as 33.3 for Ba, Co, Mn; 83.3 for Cd, Ni; 166.7 for Cu. Limits of detection were found as 0.33, 0.26, 0.27, 0.36, 0.27 and 0.19 µg L^?1 for Ba, Cd, Co, Cu, Mn and Ni, respectively. The relative standard deviations of 2.6–3.8% were obtained via nine parallel analyses. The suggested procedure was successfully validated by the analysis of TMDA-53.3 Lake Ontario water and ERM-CA022a soft drinking water certified reference materials and applied to various natural water samples.     

Ruthenium complex catalyst system for selective oxidation of cyclohexane to cyclohexanone by molecular oxygen

Summary TS-1 zeolite was successfully synthesized <Emphasis Type=Italic>in-situ</Emphasis> on a honeycomb cordierite substrate. Cu-TS-1/cordierite and LaCu-TS-1/cordierite were used as catalysts for selective catalytic reduction (SCR) of nitrogen oxides (NOx) in the exhaust of lean burn engine. High catalytic activities were obtained and the main pollutants nitrogen oxides, carbon monoxide and hydrocarbons in the exhaust could be purified together.     

Structural requirement for catalytic activity of cobalt Schiff base complex in oxygenation of alkenes

Kinetics of the oxygenation of styrene catalyzed by cobalt Schiff base complex [(Co(L)] shows that the reaction rate depends on the shape but not on the redox potential of Co(L). Magnetism of Co(L) is important for product distribution.     

Cooperative self-assembly of a macrocyclic Schiff base complex

A metal template approach affords in high yield a tetra-Zn(salphen) macrocycle (3) which shows strong and cooperative self-assembly mediated by the formation of Zn(salphen) dimer units held together via μ(2)-phenoxo interactions. A cooperative binding mode for the tetranuclear Zn(4) macrocycle 3 is supported by comparison of UV-vis and fluorescence titration data recorded for 3 when compared with respective mononuclear and dinuclear Zn(salphen) model compounds. UV-vis dilution experiments carried out for Zn(4) macrocycle 3 and its Pd(4) analogue 4, as well as comparative TEM studies involving the same tetranuclear macrocycles further support the strong assembly behavior of 3. This self-assembly seems to be primarily dictated by its ability to form multiple, self-assembled dimeric [Zn(salphen)](2) units.     

Organometallic-mediated radical polymerization using well-defined Schiff base cobalt(II) complexes

Abstract

A series of new cobalt(II) complexes of Schiff base derived from salicylaldehyde and different cycloalkylamines (cycloalkyl?=?cyclopentyl-1a, cyclohexyl-1b, and cycloheptyl-1c) was synthesized: [Co(CyPen-Salicyl)₂] (2a), [Co(CyHex-Salicyl)₂] (2b), and [Co(CyHep-Salicyl)₂] (2c). The bis(phenoxyiminato)Co(II) complexes (2a-2c) have been fully characterized by FTIR and UV–vis spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and two of the complexes were further studied by single crystal X-ray crystallography. The X-ray structure analysis of 2a-b shows that the geometry around the metal atom is a distorted tetrahedron, confirming the spectroscopic data. Electrochemical studies suggest that the redox potential of 2a-2c are sensitive to the substituent group, decreasing in order cyclopentyl?>?cyclohexyl?>?cycloheptyl. Complexes 2a-2c were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN, according to a cobalt-mediated radical polymerization (CMRP) mechanism. The VAc polymerization mediated by 2a-2c suggests that the level of control can be slightly tuned by the substitution of the cycloalkyl group on the Schiff base ligand. Complex 2b showed the smaller discrepancy between observed and calculated molecular weight, and narrower molecular weight distribution.     

Synthesis and crystal structure of a new Schiff base ligand and its cobalt(II) complex

The crystal structures of cobalt(II) Schiff base complex (Co^IIL₂ · H₂O) and Schiff base ligand 3,5-dichlorosalicylidene-2-chlorophenylmethylamine (HL) have been determined by single-crystal X-ray analysis. The geometry around cobalt in Co^IIL₂ · H₂O is distorted tetrahedral. Co^IIL₂ · H₂O crystallizes in the monoclinic system, in space group C2/c, with crystallographic parameters: a = 12.9143(16) Å, b = 8.8326(16) Å, c = 25.115(3) Å, β = 92.791(10)°, V = 2861.4(7) ų, Z = 4, F(000) = 1420, and the final R indices (I > 2σ(I)) are R ₁ = 0.0440, wR ₂ = 0.1272. HL crystallizes in the monoclinic system, in space group P2₁/c, with crystallographic parameters: a = 11.9764(15), b = 8.2331(10), c = 14.2211(17) Å, β = 98.723(6)°, V = 1386.0(3) ų, Z = 4, F(000) = 640, and the final R indices (I > 2σ(I)) are R ₁ = 0.0397, wR ₂ = 0.1018.     

Oxidative cyclisation of a tricarbonylcyclohexadieneiron complex using ferric chloride on silica gel

Treatment of the diene-Fe(CO)₃ complex (2) with dehydrated ferric chloride on silica gel support results in oxidative cyclisation of the alcohol function onto the diene ligand to give (3). This contrasts with the normal behaviour of both diene-Fe(CO)₃ complexes and alcohols toward ferric chloride.     

Oxidation using activated carbon and molecular oxygen system

This paper describes the utility of an activated carbon–molecular oxygen system, not only in the oxidation of benzylic and allylic alcohols, but also in the direct carbonylation at the benzylic position. The preparation of a variety of heteroaromatic and aromatic compounds, including substituted pyridines, pyrazoles, benzoxazoles, benzimidazoles, benzothiazoles, 2‐substituted imidazoles, indoles, pyrimidin‐2(1H)‐ones, and anthracenes, by oxidative aromatization using the activated carbon–molecular oxygen system is also discussed. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 252–267; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20152     

硅胶表面键合物的正电子湮没谱研究

本文在多孔无定形硅胶的表面上键合了不同极性的化学基团, 制成一系列相同基体, 但表面基团不同的样品, 测定了其正电子湮没寿命谱, 发现寿命谱的最长寿命组份随表面键合基不同, 寿命值有明显差别。寿命值与基团的极性及基团的体积有关, 正电子湮没谱的最长寿命组份能灵敏地表征表面的极性和化学性, 可作为表面化学定性分析的有用技术。     

Synthesis,characterization and alcohol oxidation properties of multi-wall carbon nanotubes functionalized with a cobalt(II) Schiff base complex

A hydroxyl functionalized cobalt(II) Schiff base complex has been covalently anchored to modified multi wall carbon nanotubes (MWNTs). The modified MWNTs have been characterized by physico-chemical and spectroscopic methods. The results suggest that the symmetrical Schiff base, N,N′-bis(4-hydroxysalicylidene)-ethylene-1,2-diamine; H₂[((OH)₂-salen)] acts as a tetradentate N₂O₂ donor via the deprotonated phenolic oxygens and azomethine nitrogens. The functionalized [Co((OH)₂-salen)]–MWNTs catalyze the oxidation of aliphatic and aromatic alcohols into the corresponding carboxylic acids and ketones in the presence of 30% H₂O₂ in good yields. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity over three consecutive runs).     

Silica-metalloporphyrins hybrid materials: preparation and catalysis to hydroxylate cyclohexane with molecular oxygen

Three types of novel silica-metalloporphyrins hybrid materials, Si-S-APTCPPFe, Si-S-APTCPPMn and Si-S-APTCPPCo, were prepared at room temperature by sol–gel method involving a thiol-ene polymerization reaction of 5-(4-allyloxy)phenyl-10,15,20-tri(4-chlorophenyl)porphyrin (APTCPP) with 3-mercaptopropyltrimethoxysilane (MPS). The hybrid materials were characterized by XRD, SEM, FT–IR, UV–Vis and TG, and were investigated as catalysts for the aerobic oxidation of cyclohexane. It is found that these hybrid materials are more efficient catalysts than the analogous non-supported metalloporphyrins for cyclohexane hydroxylation in metalloporphyrin–O₂–ascrobate system and the metal ion in the porphyrins significantly affected the catalytic efficiencies of these hybrid materials.     

An iron Schiff base complex loaded mesoporous silica nanoreactor as a catalyst for the synthesis of pyrazine-based heterocycles

An iron Schiff base complex was encapsulated in SBA-15 mesoporous silica to afford a Fe(III)-Schiff base/SBA-15 heterogeneous nanocatalyst for the synthesis of pyridopyrazine and quinoxaline heterocycles. These reactions proceeded in water with excellent yields. The catalyst was characterized by physico-chemical and spectroscopic methods and found to retain the characteristic channel structures of the SBA-15, allowing good accessibility of the encapsulated metal complex.